Tri-(p-aminobenzoyl) esters of pantothenyl alcohol



United States Patent 3,207,778 TRI-(p-AMINGBENZOYL) ESTERS 0FPANTOTHENYL ALCOHOL Herman Herbert Fox, Passaic, N.J., assignor toHoffman!!- La Roche Inc., Nutley, N.J., a corporation of New Jerse No Diawing. Filed Jan. 16, 1963, Ser. No. 251,752 3 Claims. (Cl. 260471)This application is a continuation-in-part of application Serial No.160,898, filed December 20, 1961, now abandoned.

This invention relates, in general, to improved cosmetic preparationsand to methods of preparing and using same. More particularly, theinvention relates both to improved aerosol hair sprays and to certainnovel esters which have been found to be particularly useful ascomponents thereof.

The expression aerosol hair spray will be used herein to denote liquidcosmetic preparations which are intended to be dispensed upon the hair,under pressure, in the form of liquid-gas aerosols. Cosmeticpreparations of this nature are well known in the art. Many of theaerosol hair sprays which are now commercially available contain a hairsetting component, the function of which is to keep the hair in setposition, or to make it manageable when it is combed or coifled. Thehair setting action of such sprays is usually attributed to the abilityof the hair setting component thereof to form a film on the hair shaftupon evaporation of the solvent vehicle.

Various hair setting components have been used in the formulation of theaerosol hair spray preparations of the prior art. These include, forexample, such materials as shellacs, ethyl cellulose, carboxymethylcellulose, gum arabic, polyvinyl alcohol, copolymers of vinyl acetateand vinylpyrrolidone. In addition, polyvinylpyrrolidone (PVP) hasproved, in the past, to be of especial importance as a hair settingcomponent of many commerically successful hair spray compositions.

It is an object of this invention to provide aerosol hair sprays havinghighly effective hair setting properties.

It is a further object of this invention to provide novel esters whichare eminently well suited for use in the formulation of aerosol hairsprays.

It is a more particular object of this invention to providetri-(p-aminobenzoyl) esters of pantothenyl alcohol as well as mixturescontaining substantial quantities of such esters.

Other objects of this invention will be obvious and will in part appearhereinafter.

It has been found that, when a trHp-aminobenzoyl) ester of pantothenylalcohol is used as a component of a hair spray formulation, preparationshaving greatly improved hair setting properties are obtained. Forconvenience, pantothenyl alcohol will be referred to, in the presentspecification and in the claims, merely aspanthenol. It is to beunderstood that, in the practice of this invention, one may employpanthenol either in the racemic or optically active form and that wherethe word panthenol is used herein it includes either and/or bothdpanthenol and dl-panthenol. Hence, the expression tri-(p-aminobenzoyl)esters of panthenol will be used herein, at various instances, todesignate either or both the tri-(p-aminobenzoyl)d panthenol and the tri(paminobenzoyl)dl-panthenol. The esters produced and used in thepreferred embodiment of this invention are prepared from dl-panthenol.

Thus, one specific embodiment of the present inven tion resides in novelpanthenol esters, that is, tri-(p-arninobenzoyl)-d-panthenol andtri-(p-aminobenzoyl)-dl panthenol, and mixtures containing substantialquantities 3,Z@7,778 Patented Sept. 21, 1965 thereof. The method ofpreparation of such esters, and of mixtures containing such esters, isalso included within the scope of the present invention. Anotherembodiment of the invention resides in novel aerosol hair spraypreparations having the novel esters, and mixtures containing same, asan essential component thereof. A further embodiment of the inventionresides in the method of setting of hair using such hair spraypreparations.

The tri-(p-aminobenzoyl) esters of panthenol which have been found to beuseful as the hair setting components of the improved hair spraycompositions of this invention are, as indicated heretofore, in and ofthemselves, novel compounds. These esters, namely,tri-(paminobenzoyl)-d-panthenol and tri-(p-aminobenzol) dlpanthenol, areprepared in the following manner: Panthenol, that is, either d-panthenolor dl-panthenol, and p-nitrobenzoyl chloride are charged into, andstirred in, a suitable reaction vessel. A ratio of about 3.0 moles ofp-nitrobenzoyl chloride is employed for each mole of panthenol used. Thereaction between these reactants is exothermic and it can be initiatedmerely by mixing same at ordinary room temperatures. However, in thepreferred practice of the invention, the reactants are mixed at atemperature which is elevated somewhat above room temperature since thisfacilitates the start of the reaction. Heating of the reaction mixtureto a temperature within the range of from about 30 C: to about 60 C. hasbeen found to be most practical. Higher temperatures can, of course, beutilized, if desired. However, for the most part, no useful purpose willbe served by mixing the reactants at a temperature of above about 60 C.Since the reaction between panthenol an dp-nitrobenzoyl chloride isexothermic, once it commences, it may be allowed to proceed tosubstantial completion without further heating. During the course of thereaction, however, the reaction mixture is continuously stirred. Whenthe reaction ceases, the product, thus obtained, is stirred for anadditional period of time at a temperature of up to about C. By means ofthis additional stirring and heating, the reaction is driven tosubstantial completion. For the present purposes, the reaction may beconsidered as complete when evolution of hydrogen chloride gas from thereaction mixture ceases. Subsequently, an inert organic solvent is addedto the reaction mixture and stirred therewith. In general, any inertorganic solvent in which the reaction product is soluble can be used,as, for example, methyl ethyl ketone, dioxane, tetrahydrofuran, etc. Thesolvent used in the preferred practice of the invention, however, isacetone. The quantity of solvent used in this step of the process is notparticularly critical. Thus, for example, one may use a quantity ofsolvent which is sufiiciently large to dissolve completely all of thereaction product. A greater or lesser quantity of solvent can be used,if desired. However, there is no particular advantage in using moresolvent than is needed to dissolve the product. On the other hand, itwill sufiice if the quantity of solvent used is such as to form aworkable slurry with the reaction mixture.

After the solvent is added to the reaction mixture, an alkali isintroduced in sufiicient quantity to neutralize the reaction mixture.Under ordinary circumstances, a ratio of one mole of alkali will beadded for each mole of p-nitrobenzoyl chloride employed in the firststep of the process. In general, any alkaline earth metal oxide,carbonate or bicarbonate, can be used as the alkali in this step of theprocess. In the alternative, any alkali metal carbonate or bicarbonatecan be used. Thus, suitable alkalis include sodium carbonate, potassiumcarbonate, calcium carbonate, sodium bicarbonate, potassium bicarbonateand calcium oxide. However, sodium bicarbonate is employed in thepreferred practice of the invention.

This step can be carried out at room temperature, or at any temperatureup to and including the reflux temperature of the mixture. The mixtureis stirred, or stirred and heated, until the evolution of carbon dioxidegas from the mixture ceases. Thereafter, the product is filtered and theinsoluble residue is Washed with acetone. The filtrate from the originalfiltration step is combined with the filtrates from the solvent washingsteps and the combined filtrate is evaporated to dryness under vacuum.

The residue, remaining after the solvent has been removed byevaporation, is principally a tri-(p-nitrobenzoyl )ester of panthenol.The residue contains also some di-(p-nitrobenzoyl) ester of panthenoland mono (p-nitrobenzoyl) ester of panthenol. This residue issubsequently dissolved in a suitable solvent. As the solvent one can usea lower aliphatic monohydroxy alcohol, such as methyl alcohol, ethylalcohol, etc., or a mixture of such alcohols. Alternatively, one canemploy a lower fatty acid ester of a lower aliphatic alcohol, such asethyl acetate, butyl acetate, ethyl propionate, etc., as the solvent. Inaddition, however, one could, if desired, use any other solvent whichdoes not react, or is not reacted upon, during the subsequent reductionstep. Tetrahydrofuran is another example of such a solvent. The product,while dissolved in such solvent, is reduced either by chemical means,for example, using either lithium aluminum hydride or aluminum amalgamas the reducing agent and employing tetrahydrofuran as a solvent, orwith hydrogen in the presence of a catalyst, such as platinum, palladiumor Raney nickel. In the preferred procedure, reduction is accomplishedby reacting the product, while dissolved in a solvent, with hydrogen inthe presence of a conventional catalytic quantity of Raney nickelcatalyst. Moreover, while in the preferred embodiment of the invention,the reduction is carried out at room temperature and at a hydrogenpressure of about 50 p.s.i., it can be carried out, if desired, at anelevated temperature and/or at under greater or lesser pressure. Afterthe reduction is complete, the reaction mixture is filtered to removethe catalyst.

By the procedure described in the preceding paragraphs, a mixture isobtained containing a substantial quantity of a tri-(p-aminobenzoyl)ester of panthenol. Such mixture comprises at least about 80% by weightof the tri-(p-aminobenzoyl) ester of panthenol and varying quantities ofthe monoand of the di-(p-aminobenzoyl) esters of panthenol. Moreover,the mixture can, and generally does, contain a relatively small amountof an alkyl ester of p-aminobenzoic acid, for example, methylp-aminobenzoate. Additionally, some extraneous compounds may be found inthe present products as impurities. The quantities of these impuritiesnormally found in the products do not affect, however, the desiredfilm-forming properties of the tri-(p-aminobenzoyl) esters of panthenol.By a refinement procedure, which will be described hereinafter, anessentially pure tri-(p-aminobenzoyl) ester of panthenol can beobtained. The expression essentially pure herein is used to connote aproduct containing at least about 92% by weight of a tri-(paminobenzoyl)ester of panthenol. In general, the product, in its essentially pureform, contains, in addition to the tri-(p-aminobenzoyl) ester ofpanthenol, relatively small quantities of the monoanddi-(p-aminobenzoyl) esters of panthenol and methyl p-aminobenzoate.

The essentially pure tri-(p-aminobenzoyl) ester of panthenol, which isreferred to in the preceding paragraph, may be obtained conveniently bythe following method. A ratio of about 3.0 moles of p-nitrobenzoylchloride and 1.0 mole of panthenol are caused to react in the mannerdescribed heretofore. The product, thus obtained, which is a mixturecontaining a substantial quantity of a tri-(p-nitrobenzoyl) ester ofpanthenol, is dissolved in a suitable solvent, following which benzeneis added thereto. In the case of the ester of dl-panthenol, the solventpreferably employed is chloroform while in the case of the ester ofd-panthenol, the solvent preferably used is methanol. Addition ofbenzene to the solvent solution results eventually in the precipitationof a white crystalline material in either case. Recrystallization ofthis crystalline product from chloroformor methanol-benzene mixturesyields the essentially pure benzene adduct of the tri-(p-nitrobenzoyl)ester of panthenol. Upon reduction of this product, in the mannerdescribed heretofore, there is obtained an essentially puretri-(paminobenzoyl) ester of panthenol.

It has been found that the film-forming properties of bothtri-(p-aminobenzoyl)-d-panthenol and tri-(p-aminobenzoyl)-dl-panthenolare such that these compounds are well suited for use as hair settingcomponents of hair spray preparations. Additionally, however, it hasbeen found that completely suitable hair spray preparations can beprepared by using products, produced as disclosed herein, containing atleast about of one of the named tri- (p-aminobenzoyl esters ofpanthenol. However, it has been observed that the film-formingproperties of the tri- (p-aminobenzoyl) esters of panthenol are somewhatenhanced as the purity of the compound is increased.

The quantities of the side reaction compounds which are present in theproducts of the invention are widely variable. For example,mono-(p-aminobenzoyl) esters of panthenol, that is, themono-(p-aminobenzoyl)-d-panthenol or themono-(p-aminobenzoyl)-dl-panthen-ol can comprise up to about 7.0% byweight of the products. In most instances, the mono-ester will comprisefrom about 0.25% to about 5.0% by weight of the product. A di-(p-aminobenzoyl) ester of panthenol, that is, thedi-(paminobenzoyl)-d-pranthenol or the di-(p-aminobenzoyl)-dl-panthenol, can comprise up to about 12.0% by weight of the products.Generally, such di-ester will comprise from about 0.25% to about 10.0%of the weight of the product. Moreover, the products can contain up toabout 7.0% by weight of an alkyl ester of p-aminobenzoic acid as, forexample, methyl p-aminobenzoate. Ordinarily, however, the products whichare produced in the preferred embodiment of the invention will containfrom about 0.25% to about 5.0% by weight of the alkyl-p-aminobenzoate.Certain other extraneous compounds may be present, as impurities in theproducts of the invention. The presence of such impurities does notadversely affect the desired film-forming properties of thetri-(p-aminobenzoyl) esters of panthenol, however, when such impuritiesdo not comprise more than about that 7.0% of the Weight of the finalroducts.

As indicated heretofore, the novel compounds of this invention, that is,the tri-(p-aminobenzoyl)-d-panthenol andtri-(p-aminobenzoyl)-dl-panthenol, or the mixtures containingsubstantial amounts of one of these esters, have been found to beespecially well suited for use as the hair setting component of hairspray preparations. These esters, or mixtures containing same, can beused as the sole hair set components of such preparations.Alternatively, these esters, or mixtures containing same, can be used inadmixture with prior art materials which perform a similar function.Moreover, these esters can be formulated with any of the adjuvantmaterials normally used in the production of conventional hair sprays.These adjuvants include, for example, erfumes, antistatic agents,auxiliary hair-conditioning agents, plasticizers, etc. Additionally, theesters, and the mixtures, of this invention are suitable for used incombination with propellants of the type generally employed in theformulation of the conventional hair spray preparations of the art. Thepreferred hair sprays of our invention, however, contain liquifiedfluorinated hydrocarbon propellants such as those marketed by E. I. duPont de Nemours & (30., Wilmington, Delaware, under the proprietarydesignation Freeon, or those marketed by Allied Chemical & DyeCorporation, New York, New York, under the proprietary designationGenetron, or those marketed by Pennsalt Chemicals Corporation,Philadelphia, Pennsylvania, under the protions.

prietary designation Isotron. Useful propellants are those made bycompounding mixtures of various Freon products, for example, Freon 11(trichloromonofiuoromethane), Freon 12 (dichlorodifluoromethane) andFreon 114 (symmetrical dichlorotetrafluoromethane). Especially usefulare mixtures of Freon 11 and Freon 12 and of Freon 12 and Freon 114 inthe proportions recommended by the manufacture for pressure ranges of 12to 60 p.s.i.g.

The finished hair spray preparations of this invention are readilyprepared. The novel panthenol ester hair setting component, thepreparation of which has been described heretofore, together with suchoptional ingredients as the formulator may wish to employ, that is, theperfume, antistatic agent, auxiliary hair-conditioning agent, etc., alsoreferred to heretofore, are dissolved in a suitable solvent to form whatwill be designated herein as a concentrate. Prefenably, a lowermolecular weight aliphatic alcohol, such as ethanol, is used inproducing the concentrate. The amount of alcohol used may vary within arather wide range. Generally, a sufiicient quantity of solvent will beused to provide a concentrate containing from about 1.0% to about 10.0%by Weight of the novel hair setting component of this invention. Adenatured alcohol, for example, the solvent known in the art as SDA N0.40 alcohol (anhydrous) is used in the preferred embodiment of theinvention. Anhydrous solvents are employed to advantage, particularlywhen corrosion of the container presents a problem. The concentrate andthe propellant are then packaged into a suitable dispenser by any knownor convenient method.

The ratio of concentrate to propellant in the hair spray compositions ofthe invention can be varied over a rather wide range. Gene-pally, :aweight proportion of about 1.0 part of concentrate for each 2.0 parts ofpropellant is employed, when such ratio will rovide a finished hairspray preparation containing from about 0.25% to about 10.0% by weightof the hair setting component.

The concentrate and the propellant can be packaged, by any known method,in aerosol container-dispensers of the type ordinarily employed in salesto the consumer. For example, the concentrate and the propellant can bepackaged by the so-called cold-fill method of packaging. In this method,the concentrate is cooled to a temperature of about 0 C., and chargedinto a suitable aerosol container. The propellant, previously cooled toabout l0 C., is then added to the container, following which thecontainer is tightly sealed with a lid having some suitable valvethrough which the product, in the form of a spray, can be dispensed. Theforegoing method of filling the aerosol container is exemplary only, itbeing fully understood that the present invention is not restricted tothis particular method of packaging. For

. example, if desired, the so-called pressure-fill method of packagingcan be used.

The novel tri-(p-aminobenzoyl) esters of panthenol, described hereinare, in part, characterized by the fact that, in the form of an alcoholsolution, they form nontacky and non-hygroscopic films. These estersare, as indicated heretofore, further characterized by the fact thatthey are well suited for use as the hair set ingredient of hair spraypreparations. In addition to their outstanding hair setting properties,however, certain other advantages accrue from the use of these esters inhair spray prepara- In the first place, hair sprays containing theseesters show little or no tendency to flake when applied to the hair.Moreover, these esters have been found to possess sun screen activityand, as a result, the films formed thereby will protect the hair fromundesired bleaching by the sun. Moreover, since the films formed bythese esters are non-hygroscopic, hair treated therewith tends to beheld in place more effectively, particularly under conditions of highhumidity. However, the esters can be washed out of the hair readily bymeans of the use of conventional soaps and shampoos.

The preferred method of making the novel tri-(pamir1obenzoyl) esters ofpanthenol of this invention is as follows: Panthenol, that is, eitherd-panthenol or dl-panthenol, is reacted with p-nitrobenzyol chlorideusing a ratio of about 3.0 moles of p-nitrobenzoyl chloride for eachmole of panthenol. To the reaction product, thus obtained, there isadded an inert organic solvent and an alkali, such as an alkaline earthmetal carbonate, bicarbonate or oxide or an alkali metal carbonate orbicarbonate. The reaction mixture is filtered, the solid remaining onthe filter is washed with solvent, the filtrate and washings arecombined and solvent is then removed by evaporation. The residue whichremains after the solvent has been removed, said residue comprisingpredominantly tri-(pnitrobenzoyl)-d-panthenol or tri(p-nitrobenzoyl)-dlpanthenol depending upon whether d-panthenol or d1-panthenol was used initially, is subjected to catalytic reduction, byany suitable method, while dissolved in a lower aliphatic alcoholsolvent, a lower aliphatic ester or tetrahydrofuran. Optionally, theproduct may be purified, by way of its benzene adduct, prior to itsreduction. The reduction product can be separated from the solvent byany convenient means. By this method, there is obtained a product,non-hygroscopic in nature, which contains a substantial quantity, thatis, by weight or more of the tri-(p-aminobenzoyl)-panthenol. Such ester,or mixture containing such ester, has been found to be well suited foruse as a hair set ingredient of a hair spray preparation.

For a fuller understanding of the nature and objects of this invention,reference may be had to the following examples which are given merely asfurther illustrations of the invention and are not to be construed in alimiting sense. All parts given in the examples are parts by weightunless otherwise indicated.

EXAMPLE 1 In this example, 0.1 mole of d-panthenol and 0.3 mole ofp-nitrobenzoyl chloride were charged into a reaction vessel and themixture was stirred and warmed until the components thereof commenced toreact exothermically. The reaction was permitted to proceed,spontaneously, until the exothermic reaction ceased. The reactionproduct, while being stirred, was then warmed on a steam bath toliberate hydrogen chloride gas. When the hydrogen chloride gas wasliberated, the reaction product was dissolved in about 200 cc. ofacetone and 0.3 mole of sodium bicarbonate was added to the acetonesolution. The reaction mixture was then heated to reflux and it wasmaintained at reflux temperature for a period of about 30 minutes. Thewarm solution was filtered and the undissolved material which wasretained on the filter was washed with acetone. The filtrate from thefirst filtration step was combined with the filtrate from the acetonewashing step and the solution was, thereafter, evaporated to drynessunder vacuum. The residue remaining after the solvent was removed, saidresidue comprising predominantly tri-(p-nitrobenzoyl)-d-panthenol, wasdissolved in ethanol and reduced with hydrogen, at room temperature andusing 50 p.s.i. hydrogen pressure, in the presence of Raney nickelcatalyst.

When reduction of the product was: complete, the reaction mixture wasfiltered to remove the catalyst. The filtrate was evaporated to drynessto yield the desired product in the form of a non-hygroscopic glass.

The product which was thus obtained was a mixture comprising about byweight of tri-(p-aminobenzoyl)- d-panthenol, about 8.0% by weight ofdi-(p-aminobenzoyl)-d-panthenol and about 1.0% by weight of methylp-aminobenzoate. This product was comminuted to a fine powder.

EXAMPLE 2 0.1 mole of dl-panthenol and 0.3 mole of p-nitrozenzoylchloride were charged into a reaction vessel and the mixture was stirredand warmed until the components thereof commenced to reactexothermically. The reaction was permitted to proceed, spontaneously,until the exothermic reaction ceased. The reaction product, while beingstirred, was then warmed on a steam bath to liberate hydrogen chloridegas. When the hydrogen chloride gas was liberated, the reaction productwas dissolved in about 200 cc. of acetone and 0.3 mole of sodiumbicarbonate was added to the acetone solution. The reaction mixture wasthen heated to reflux and it was maintained at reflux temperature for aperiod of about 30 minutes. The warm solution was filtered and theundissolved material which was retained on the filter was washed withacetone. The filtrate from the first filtration step was combined withthe filtrate from the acetone washing step and the solution was,thereafter, evaporated to dryness under vacuum. The residue remainingafter the solvent was removed, said residue comprising predominantlytri-(p-nitrobenzoyl)-dlpanthenol, was dissolved in methanol and reducedwith hydrogen, at room temperature and using 50 psi. hydrogen pressure,in the presence of Raney nickel catalyst.

When reduction of the product was complete, the reaction mixture wasfiltered to remove the catalyst. The filtrate was evaporated to drynessto yield the desired product in the form of a non-hygroscopic glass.

The product which was obtained was a mixture containing a substantialquantity of tri-(p-aminobenzoyl)-dlpanthenol. The mixture was comprisedof about 82% by weight of tri-(p-aminobenzoyl)-dl-panthenol, about byweight of di-(p-aminobenzoyl)-dl-panthenol, about 0.5% by weight ofmono-(p-aminobenzoyl)-dlpanthenol and about 2.0% by weight of methylp-aminobenzoate. This product was non-hydroscopic in nature andalcoholic solutions thereof, when sprayed in a thin layer, formednon-tacky films.

EXAMPLE 3 In this example, 30.6 grams (0.15 mole) of dl-panthenol and84.0 grams (0.45 mole) of p-nitrobenzoyl chloride was gently warmed on asteam bath until a vigorous reaction was initiated during which heat andhydrogen chloride gas were evolved. Once the reaction began, theapplication of external heat was discontinued. The reaction mixture wasallowed to react until the spontaneous reaction began to subside.Thereafter, the reaction mixture was heated to a temperature of about 90C., with stirring. Such heating and attendant stirring was continueduntil the evolution of the gaseous hydrogen chloride ceased. To insurethat the reaction had gone to completion, the clear, viscous reactionproduct was dissolved in 300 cc. of acetone and 35.0 grams of sodiumbicarbonate was added to that solution. The mixture, thus obtained, wasstirred until no carbon dioxide was evolved. The mixture was filtered,the insoluble salt was washed with acetone and the filtrate and theacetone washings were combined. The combined filtrate and acetonewashings were then heated under vacuum to remove the solvent. A viscousresidue was obtained which, on cooling, set to a soft glass which couldnot be crystallized and was only slightly soluble in methanol. Infra-redanalysis, showing a secondary amide, nitro and ester functions, but nohydroxy groups, was interpreted as indicating that the product wascomprised substantially of tri-(p-nitrobenzoyl)-dl-panthenol. This esterwas dissolved in a minimum of chloroform, following which benzene wasadded to the solution. Addition of the benzene caused the precipitationof a white, crystalline material which, upon crystallization fromchloroform-benzene mixtures, formed crystal clusters, melting, withdecomposition, at 148 150 C., corrected. The crystalline product, thusobtained, was predominantly the benzene adduct oftri-(p-nitrobenzoyl)-dl-panthenol. Analysis.Calculated for C H N O -C HMolecular weight 731. Theory: C, 59.1%; H, 4.7%; N, 7.7%. Found: C,59.2%; H, 4.4%; N, 7.5%.

The foregoing procedure was repeated several times and the productsobtained were examined by thin-layer chromatography on silica gel G,using a heptane-ethyl acetate system in a volume of 4:6, with thefollowing results:

Table I Percent Unidentified (R; 0.0; 0.5; 0.7)

Percent Di-(pnitrobcnzoyl)-dlpan thenol-B enzene Adduct-(Rr 0.3)

Percent Tri-(pnitrobcnzoyD-dlpanthenol-B enzene Adduct-(Rr 0.6)

(DZOO 9 w UICIIUI The substantially pure, crystalline benzene adduct oftri-(p-nitrobenzoyl)-dl-panthenol, melting at 148-150 C., corrected,produced in this example (14.6 grams) was partially dissolved in 150 cc.of ethyl acetate and it was reduced with hydrogen using Raney nickelcatalyst. Hydrogen uptake ceased and reduction was complete in aboutthirty minutes. The catalyst was filtered OE and the solvent was removedunder vacuum to yield 11.0 grams of product,

E fi max. 294/5 m,u=1111 II III In Table II:

Column I represents percent tri-(p-aminobenzoyl)-dl-pauthenol (Rf 0.6)

Column 11 represents percent di-(p-aminobenzoyl)-dlpanthenol (R; 0.7)

Column III represents percent mono-(p-aminobenzoyl)- dl-panthenol (R0.4)

Column IV represents percent methyl p-aminobenzoate Column V representspercent other (unidentified impurities) (R, 0.0; 0.1; 0.8)

Each of the products identified in Table II were comminuted to a finepowder.

EXAMPLE 4 A mixture was prepared using 0.5 part by weight of the productproduced in Example 1 and 0.2 part by weight of a perfume oil. Aconcentrate was prepared by dissolving this mixture in 32.3 parts byweight of SDA No. 40 alcohol (anhydrous).

A propellant was prepared by mixing 60.0 parts by weight of Freon 11 and40.0 parts by weight of Freon 12.

The propellant and the concentrate were then packaged in an aerosolcontainer-dispenser. The container-dispenser employed comprised: (a) aconventional aerosol can, 6 oz. capacity, side seam lead solderedoutside, round dome top with 1" curled opening, concave bottom, halfpound electrolytic tin plate throughout, no internal coating; (b) anassembled cup-type valve (e.g. Model NN,

Precision Valve Corporation, Yonkers, New York), ineluding apolyethylene, mechanical break-up press button and polyethylene diptube; and (c) a protective dome (e.g. Model 5, Precision ValveCorporation, supra). A suitable form of container-dispenser is thatshown diagrammatically in FIGURE 7 at page 800 of Cosmetics Science andTechnology (ed. Edward Sagarin), published by Interscience Publishers,Inc., New York, N.Y., 1957.

The filling method employed was the so-called coldfill method ofpackaging. The concentrate was cooled to C. and 33.0 parts by weightthereof charged into the aerosol container-dispenser. Thereafter, 67.0parts by weight of the propellant, previously cooled to a temperature ofabout 10 C., were then added to the conminer-dispenser. Valves wereinserted into the filled cans and these were crimped on. The hair spraypreparation, thus obtained, was evaluated by the following method: Hairswatches were wetted with water and put into curlers. The hair swatcheswere subsequently dried and then sprayed with the hair spray preparationproduced as disclosed herein. Each swatch was sprayed six times from adistance of about eight inches.

Evaluation of the product by this method proved it to have highlyeffective hair setting properties.

EXAMPLE A mixture was prepared using 1.0 part by weight of the productproduced as described in Example 2 and 0.2 part by weight of a perfumeoil. A concentrate was prepared by dissolving the mixture, thusobtained, in 31.8 parts by weight of SDA No. 40 alcohol (anhydrous).

The propellant was prepared by mixing 60.0 parts by weight of Freon 11and 40.0 parts by weight of Freon 12.

The propellant, in the amount of 67.0 parts by weight, and theconcentrate, in the amount of 33.0 parts by weight, were packaged in anaerosol container-dispenser by the cold-fill method described in Example3.

The product of this example was evaluated as a hair spray by the methoddescribed in Example 3. By this method of evaluation, the preparationwas found to possess highly effective hair setting properties.

EXAMPLE 6 A mixture was prepared using 2.0 parts by weight of theproduct produced as described in Example 2 and 0.2 part by weight ofperfume oil. A concentrate was prepared by dissolving this mixture in30.8 parts by weight of SDA No. 40 alcohol (anhydrous).

A propellant was prepared by mixing 60.0 parts by weight of Freon 11 and40.0 parts by weight of Freon 12.

Thereafter, 33.0 parts by weight of the concentrate and 67.0 parts byweight of the propellant were packaged in an aerosol container-dispenserby the cold-fill method described in Example 4.

The hair spray preparation, thus obtained, was evaluated by the methoddescribed in Example 4. By this method of evaluation, the preparationwas found to possess highly effective hair setting properties.

EXAMPLE 7 In this example, 0.2 part by weight of a perfume oil was addedto, and mixed with, each of the three tri- (p-arninobenzoyl)dl-panthenolesters described in Table II of Example 3. In each instance, the perfumewas added to 2.0 parts by weight of tri-ester. Separate concentrateswere prepared by dissolving each of the three mixtures in 30.8 parts byweight of 50A No. 40 alcohol (anhydrous).

A propellant was prepared by mixing 60.0 parts by weight of Freon l1 and40.0 parts by weight of Freon 12.

Thereafter, 33.0 parts by weight of each of the concentrates, previouslydescribed, and 67.0 parts by weight of the propellant, were packaged ineach of three aerosol container-dispensers by the cold-fill methoddescribed in Example 4.

The hair spray preparations, thus obtained, were evaluated by the methoddescribed in Example 4. By this method of evaluation, the preparationswere found to possess highly effective hair setting properties.

I claim:

1. Tri-(p-aminobenzoyl) ester of pantothenyl alcohol.

2. Tri-(p-aminobenzoyl) ester of d-pantothenyl alcohol.

3. Tri-(p-aminobenzoyl) ester of dl-pantothenyl alcohol.

References Cited by the Examiner UNITED STATES PATENTS 610,348 9/98Einhorn 260--471 1,903,880 4/33 Sander 260-471 2,793,980 5/57 Mamlok etal 16787.1 2,836,543 5/58 Watson 16787.l

FOREIGN PATENTS 23 8,597 11/ Switzerland.

646,758 11/50 Great Britain.

LEON ZITVER, Primary Examiner.

FRANK CACCIAPAGLIA, JR., DANIEL D.

HORWITZ, Examiners.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No '5, 2O78 September 21, 1965 Herman Herbert POX It is hereby certified thaterror appears in the above numbered patent requiring correction and thatthe said Letters Patent should read as corrected below.

Column 2, line 14, for "trl- (p-aminobenzol) d1 read triwlfpaminobenzoyl) -d1- w line 2?, for "30" C3" read 50 Ct line 32 for "andp-nitro" read M and p-nitrocolumn 4, line 19, for (p-aminobenzoyl" readH (p-' amino benzoyl) line 65, for "used" read I a use column 6, line74, for: p-nitrozenzoyl" read w p-nitrobenzoyl column Y line 53, for"nun-hydroscopic" read non hygroscopic: H I

Signed and sealed thls 28th day of June 1966 I (SEAL) Attest:

ERNEST W. SWIDER EDWARD J. BRENNER Attesting Officer Commissioner ofPatents

1. TRI-(P-AMINOBENZOYL) ESTER OF PANTOTHENYL ALCOHOL.